Cyclic urea amide phosphates useful as insecticides

ABSTRACT

A NEW CLASS OF CYCLIC UREA AMIDE PHOSPHATES AND PHOSPHONATES, UTILIZED AS INSECTICIDES, AND HAVING THE FOLLOWING GENERAL STRUCTURE COVERING THE COMPOUNDS OF THIS INVENTION:   OC&lt;(-N(-A)-CH2-(CH2)N-CH2-N(-CO-CH2-B)   WHEREIN N=O, 1   A=H; (R-O-)2-P(=X)-CH2-CO-; OR R-O-P(=X)(-R)-S-CH2-CO-;   B= (R-O-)2-P(=X)-S-; OR R-O-P(=X)(-R)-S-   AND WHEREIN R=LOWER ALKYL GROUP HAVING 1-5 CARBON ATOMS; X=O OR S.

United States Patent 3,629,280 CYCLIC UREA AMIDE PHOSPHATES USEFUL ASINSECTICIDES Peter E. Newallis, Overland Park, Kans., assignor to AlliedChemical Corporation, New York, N.Y. No Drawing. Filed Dec. 29, 1967,Ser. No. 694,418 Int. Cl. C07d 49/30 [7.5. Cl. 260309.7 4 ClaimsABSTRACT OF THE DISCLOSURE A new class of cyclic urea amide phosphatesand phosphonates, utilized as insecticides, and having the followinggeneral structure covering the compounds of this invention:

and wherein R=lower alkyl group having 1-5 carbon atoms; X=O or S.

BACKGROUND OF THE INVENTION This invention relates to a new class ofphosphates and phosphonates useful as insecticides and acaricides and inparticular to a new class of cyclic urea amide phosphates andphosphonates.

The requirements for useful insecticides and acaricides vary dependingupon the kind of application intended. To be successful, an insecticidemust, of course, be toxic to the insect or acarid to be controlled. Forsome applications, it is desirable that the insecticide be stable andhave extended residual activity; for other applications, it is desirablethat its useful life be short. When the insecticides are used byunskilled personnel, it should be relatively non-toxic to mammals, inother cases, particularly where it is to be applied only by skilledpersonnel, the mammalion toxicity is less of a factor. Of course, wherethe insecticide is to be applied to the foliage or roots of plants, orto soil in which the plant is growing, it must be non-phytotoxic, atleast at the insecticidal dosage.

It is an object of this invention to provide a new class of phosphatesand phosphonates as insecticides.

It is another object of this invention to provide a new class of cyclicurea amide phosphates.

It is an additional object of this invention to provide a method forproducing a new class of cyclic urea amide phosphates.

3,6292% Patented Dec. 21, 1971 SUMMARY OF THE INVENTION and whereinR=lower alkyl group having 1-5 carbon atoms; and X=O or S.

These compounds are viscous liquids which are soluble in many organicsolvents but are essentially insoluble in water. They have anoutstanding acaricidal activity, and are characterized by low toxicityfor warmblooded animals. Accordingly, they can be used safely and veryeffectively for combatting eggs and active stages of spider mites in theprotection of plants. These compounds can also be used as activetoxicants in compositions for the control of a number of insectorganisms such as flies, beetles, worms, roaches, cattle grubs, andaphids. Furthermore, the toxic potency of this class of compounds issuch as to permit their effective use as dilute solutions in soaps,sprays, paints, and oils.

Generally the synthesis of this class of compounds may be carried out byreacting a urea chloroacetamide with an ammonium salt of an alkylphosphorothioate or dithiophosphate as illustrated by the followingreaction:

wherein n, A, B, R, and X have the same significance as indicated above.The reaction may be carried out in any common inert organic solvent suchas acetone, benzene, dimethylformamide or carbon tetrachloride.Approximate stoichiometric amounts of the reactants are used. Themixture is refluxed for 14-36 hours and preferably from 20- 30 hours.The acetone or other solvent is then removed by distillation underreduced pressure and the residue is extracted by adding methylenechloride or other suitable extractive compound. The methylene chloridesolution is then washed with water and separated out. Finally, theorganic solution is dried and the methylene chloride is removed bydistillation to leave the residue product.

3 DESCRIPTION OF THE PREFERRED EMBODIMENT Preparations of typicalcompounds of the invention are described in the following example. Theexamples are intended to be illustrative and are not to be considered aslimiting the invention in any way.

EXAMPLE I A solution was prepared by adding 8.1 grams of ethyleneurea-a-chloroacetamide to 100 ml. of acetone. Then 9.5 grams ofS-ammonium 0,0-diethyl phosphorothioate were added to the solution. Thesolution was then refluxed for over a 24 hour period. At this point theacetone was removed by distillation under reduced pressure leaving theresidue. The product was extracted from the residue by the addition of100 ml. of methylene chloride. The methylene chloride solution was thenwashed with 50 ml. of water and the organic solution was separated fromthe aqueous solution. The organic solution was dried and the methylenechloride solvent was removed by distillation in vacuum. The residueproduct, N-(0,0- diethylphosphorothioxyacetyl ethyleneurea), which islisted in Table I as Compound 3, weighed 13.5 grams. This product wasinsoluble in water and soluble in acetone.

Table I lists other compounds of this invention which were prepared by amethod similar to that used in Example I.

TABLE I Compound Number Compound S O O 0 II N i H II S O O O u n i i u uenant! SCIhC-N TABLE ICoutinuetl Compound Number Compound it i l i ll(CH3O)zlSCH1CN N-CCHzSl(OCH i l i i (C1H O)2PS-CH2CN NCCHzSl(OC2lI \H/ OIn using the compounds of this invention as insecticides, theundesirable organism may be killed by contactmg the insect directly, bycontacting the insect through its habitat, or by contacting the insectthrough its food prior to ingestion with toxic amounts of the compounds.Standardized tests were conducted to determine the effectiveness asinsecticides of the compounds listed in Table I against adult houseflies (HFA), two-spotted spider mites (TSSM), Mexican bean beetle larvae(MBBL), pea aphid adults (FAA), and southern armyworm larvae (SAL).

The following non-systemic tests were performed to illustrate theeffectiveness of the compounds of Table '1.

Test I.Non-systemic primary test for Mexican bean beetle larvae (MBBL) Asolution consisting of 4.8 gm. of Compound 1 was mixed in cc. ofacetone. The solution was diluted with water so that the concentrationof Compound 1 was /2 oz./l00 gal.

Horticultural (cranberry) bean plants, in 2 inch pots with all foliageremoved except one primary leaf, were sprayed with the solution for 2seconds 'on the upper surface and 5 seconds on the under surface. Thespray was delivered from a De Vilbiss atomizer nozzle at 20 p.s.i. Theapproximate volume of spray on the upper surface was 0.19 cc. and theunder surface was 0.48 cc. After spraying the deposits were allowed todry on the plants and 5 3rd instar larvae were then confined on eachplant with 6 inch screen wire spheres. Mortality and feeding recordswere made 3 days after treatment.

Test II.Non-systemic test for pea aphid adults (FAA) A solutionconsisting of 4.8 grams of Compound 1 was mixed in 100 cc. of acetone.The solution was diluted with water so that the concentration ofCompound 1 was /2 oz./l00 gal.

English broad bean plants were sprayed for 2 seconds on upper surfaceand 5 seconds on under surface with this solution. Adult female aphides(10 per test) were brushed from infested broad bean plants into 5 inchscreen wire hemispheres and sprayed for 5 seconds (approx. 0.6 cc.delivery per second from nozzle). Spray was applied from a DeVilbissatomizer nozzle at 20 p.s.i., with the aphids 15 inches from the nozzle.Following treatment, aphids were caged over previously sprayed plantsand mortality records were usually made 3 days later.

Test III.-Non-systemic primary test for southern armyworm larvae (SAL) Asolution consisting of 4.8 gins. of Compound 1 was mixed in 100 cc. ofacetone. The solution was diluted with water so that the concentrationof Compound 1 was 4 oz./100 gal.

Horticultural (cranberry) bean plants, in 2 /2 inch pots with allfoliage removed except one primary leaf, were sprayed with the solutionfor 2 seconds on the upper surface and 5 seconds on the under surface.The spray was delivered from a DeVilbiss atomizer nozzle at 20 p.s.i.The approximate volume of spray on the upper surface was 0.19 cc. andthe under surface was 0.48 cc. After spraying, the deposits were allowedto dry on the plants and 4th and 5th instar larvae were then confined oneach plant with 6-inch screen wire spheres. Mortality and feedingrecords were made 3 days after treatment.

Test IV.Non-systemic primary test for two-spotted spider mites (TSSM) Asolution was prepared of 4.8 gm. of Compound 1 in 100 cc. of actone. Thesolution was diluted with Water to a concentration of 4 oz./100 gal. ofCompound 1.

Young horticultural (cranberry) bean plants in 2 /2 inch pots wereinfested with mites (all stages) one day before treatment. In treatingplants the upper surfaces was sprayed with the solution for two secondsand the lower or under surface was sprayed for 5 seconds. The spray wasdelivered from a DeVilbiss atomizer nozzle operated at 20 p.s.i. withthe plant about 18" from nozzle. The approximate volume of spray on theupper surface was 0.13 cc. and' on the lower surface was 0.21 cc.Following the treatment, the potted plants were placed in irrigatedtrays in the greenhouse and initial kills of adults were recorded threedays later. Residual and ovicidal observations were made 7-8 days aftertreatment, which allowed ample time for the eggs to hatch undergreenhouse conditions. One leaf from each plant was used to make 3-daycounts, and the remaining leaf on each plant was used to determineresidual and ovicidal activity.

Test V.-Non-systemic primary test for house fiy adults (HFA) Dry food (6parts powdered non-fat dry milk, 6 parts granulated sugar and 1 partpowdered egg) was mixed with an acetone solution of Compound 1 so thatthe food contained 0.125% of the compound. The mixture was allowed todry and then repulverized. Wettable powders were mixed with the dry foodwith the aid of mortar and pestle. The treated food was placed inemergence cages containing 50 fly pupae. Cages containing untreated foodwere used as checks. Examination of each cage was made periodically for8 days to determine emergence, condition of flies, and acute toxicity.

Similar tests were performed for Compounds 2 and 10, the results ofwhich are also disclosed with Compound 1 in Table II. It should be notedthat with the exception of the southern armyworm larvae the compoundstested were on the whole very effective.

The same compounds were then put through systemic primary tests. Thesystemic primary tests were conducted for MBBL, PAA, SAL, and TSSM.

TABLE II.RESULTS OF NON-SYSTEMIC PRIMARY TESTS 1 No live young. NoTE.**E.R.=Excellent residual; N.0.R.=No ovicidal or residual.

Test VI.Systemic primary test for Mexican bean beetle larvae (MBBL) Astandard acetone solution containing 4.8 grams of Compound 1 per 100 cc.of acetone was diluted with water to 4 oz./100 gals. of H 0. Afterdilution, 100 cc. of the solution were placed in glass jars, along withthe test plants (young horiticultural (cranberry) bean plants) whoseroots had been Washed free of soil. The roots of the test plants were incontact with the bottom of the container. Aluminum foil was fitted overthe top of the container and around the stem of the plant to lessenpossible fumigant effects of the compounds tested. The insects wereplaced on the plants within 24 hours after treatment and the mortalityrecords were made 3 days later.

Test VII.System primary test for pea aphid adults (PAA) A standardacetone solution containing 4.8 grams of Compound 1 per cc. of acetonewas diluted with water to 4 oz./ 100 gals. H O. After dilution, 100 cc.of the solution were placed in glass jars, along with the test plants(young English broad bean plants) whose roots had been washed free ofsoil. The roots of the test plants were in contact with the bottom ofthe container. Aluminum foil was fitted over the top of the containerand around the stem of the plant to lessen possible fumigant effects ofthe compounds tested. The insects were placed on the plants within 24hours after treatment and the mortality records were made 3 days later.

Test VIII.Systemic primary test for southern armyworm larvae (SAL) Astandard acetone solution containing 4.8 grams of Compound 1 per 100 cc.of acetone was diluted with water to 4 oz./ 100 gals. of H 0. Afterdilution, 100 cc. of the solution were placed in glass jars, along withthe test plants (young horticultural (cranberry) bean plants) whoseroots have been washed free of soil. The roots of the test plants werein contact with the bottom of the container. Aluminum foil was fittedover the top of the container and around the stem of the plant to lessenpossible fumigant effects of the compound tested. The insects wereplaced on the plants within 24 hours after treatment and the mortalityrecords were made 3 days later.

Test IX.Systemic primary test for two-spotted spider mites (TSSM) Astandard acetone solution containing 4.8 grams of Compound 1 per 100 cc.of acetone was diluted with water to 4 oz./ 100 gals. of H 0. Afterdilution, 100 cc. of the solution were placed in glass jars, along withthe test plants (young horticultural (cranberry) bean plants) whoseroots had been washed free of soil. The roots of the test plants were incontact with the bottom of the container. Aluminum foil was fitted overthe top of the container and around the stem of the plant to lessenpossible fumigant effects of the compounds tested. The insects wereplaced on the plants within 24 hours after treatment and the mortalityrecords were made 3 days later. The ovicidal and residual data wasrecorded 8 days after the treatment.

The results of Tests VI-IX for compounds 1,2, and 10 are listed in TableIII.

It is noted that the compounds were not very effective against MBBL andSAL but very effective against PAA and TSSM.

The illustrations of the compounds that constitute the invention givenabove are not intended to limit the invention in any way but are merelydescriptive. All modifications which fall within the spirit of thepresent invention are claimed as part of the present invention.

TABLE III.RESULTS OF SYSTEMIC PRIMARY TESTS 1 No living young on testplants.

N0rE.-N.R. =no residual; F. R. =fair residual; G. R. =good residual.

7 8 I claim: References Cited 1. Acompound f thfi formula: UNITED STATESPATENTS 2,852,514 9/1958 Schrader et al. 260326.5 A 1 2,706,194 4/1955Morris et a1. 260244 R0 21 scH,-oN N CH1 P O 2,914,530 11/1959 Schraderet a1. 260248 J5 4', 3,134,801 5/1964 Sehring et a1. 260 -326.5 A 113,232,987 2/1966 Lutz et a1. 260561 P 3,406,179 /1968 Jamison 260309] 10FOREIGN PATENTS wherein: R=alkyl of 1-5 carbon atoms; and X=O or S.

5/1955 France 260309.5

2. A compound as claimed in claim 1 wherein R repre- 1 O93,728

sents ethyl.

3. A compound as claimed in claim 1 wherein R repre- NATALIE TROUSOFPumary Exammer sents methyl.

4. A compound as claimed in claim 1 wherein R repre- 15 sents ethyl andX represents S. 260 1 P; 42425 1, 273

PC4050. 5 "UNITED STATES PATENT OFFICE I lnv'entdfls) PETER E. NEWALLlS151's cerizifi ed thsberror apoears in the above-identified patentandthat said Letters Patent are hereby corrected as shown below:

(SEE ATTACHED SHEET FOR CONCLUSION) 1 Page '2 'of 2 Pages Po-wso UNITEDSTATES PATENT- OFFICE (5 CERTIFICATE OF CORRECTION Patent No. 3, 629,280I Dated Decernber 21. 1971 lnventmds) PETER E. .NEWALLIS It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below: 1

T should be s. o o F ll CH3O)2PSCH2C N\b/N c c11 s1=(ocn Column 5, line18, "0.21" should be +0.32

Column 6, line 4, "System" should be -Syste1hic-- Signed and seals (3this 23rd day of May 1972'.

(:E AL) Auto-st:

EDWQXRIU E-'E.FIETCI'1ER,JR. ROBERT GOTTSCHALK Abbe: ting OfficerCommissioner of Patents

